WO2010059587A1 - Valorisation d’une huile brute acide utilisant des cavitations et des systèmes à base de filtration - Google Patents

Valorisation d’une huile brute acide utilisant des cavitations et des systèmes à base de filtration Download PDF

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Publication number
WO2010059587A1
WO2010059587A1 PCT/US2009/064690 US2009064690W WO2010059587A1 WO 2010059587 A1 WO2010059587 A1 WO 2010059587A1 US 2009064690 W US2009064690 W US 2009064690W WO 2010059587 A1 WO2010059587 A1 WO 2010059587A1
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Prior art keywords
crude oil
stream
cavitation
oil feed
catalyst
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PCT/US2009/064690
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English (en)
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M. Rashid Khan
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Saudi Arabian Oil Company
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Publication of WO2010059587A1 publication Critical patent/WO2010059587A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects

Definitions

  • the present invention relates to the conversion of heavier sulfur-containing crude oil into lighter crude oil with lower sulfur content and lower molecular weight than the original crude oil.
  • the invention generally relates to a process for treating a heavy hydrocarbon crude oil, also referred to herein as "crude oil.” More particularly, the process described herein is directed to upgrading a heavy hydrocarbon crude oil feedstock by a hydroprocessing catalyst assisted hydrotreatment.
  • hydroprocessing catalyst assisted hydrotreatment Although the term hydrocracking is often applied to these types of processes, the term hydroconversion (or hydroprocessing or hydrotreatment) will be used herein to avoid confusion with conventional gas oil hydrocracking.
  • Heavy crude oils are composed chemically of a very broad range of molecules differing widely in molecular weight (MW) and chemical properties.
  • MW molecular weight
  • heavy crude oils from different formations and locations around the world have different characteristics.
  • various separation procedures are used to break down the feed into a number of smaller fractions that are more consistently identifiable.
  • One such technique involves separation into solubility classes using solvents of varying polarity and further separation using column chromatography. These fractions can then be further characterized in terms of an average structure by nuclear magnetic resonance (NMR) or other analytical technique known to persons skilled in the art.
  • NMR nuclear magnetic resonance
  • heavy crude oils range widely in their composition and physical and chemical properties, they are typically characterized by having a relatively high viscosity, high boiling point, high Conradson carbon residue, low API gravity (generally lower than 25), and high concentration of sulfur, nitrogen, and metallic impurities. Additionally, the hydrogen to carbon ratio of heavy crude oils is lower than desirable. Further, much of the crude oil around the world also contains relatively high concentration of sulfur.
  • crude oil, or heavy crude oil is understood to include heavy hydrocarbon crude oil, tar sands, bitumen, and residual oils, i.e., bottom of the barrel or vacuum bottom oils.
  • Petroleum hydrocarbons are subjected to a variety of physical and chemical processes to produce higher value products.
  • a gas-oil separator GOSP
  • crude is processed to remove water and other contaminants, such as salt, to achieve BS&W requirements.
  • BS&W requirements are a measure of bottom sediment and water, usually expressed as a percentage by weight.
  • Hydrogen addition processes involve reacting heavy crude oils with an external source of hydrogen resulting in an overall increase in hydrogen to carbon ratio.
  • Examples of hydrogen addition processes include: catalytic hydroconversion (hydrocracking) using active HDS catalysts; fixed bed catalytic hydroconversion; ebullated catalytic bed hydroconversion; thermal slurry hydroconversion (hydrocracking); hydrovisbrealdng; and hydropyrolysis.
  • Feedstock from the oil field typically contains water.
  • Processed oil that is to be transported by pipeline must generally be free of water to meet pipeline specification.
  • processed oil must generally be free of water to be sold.
  • a large portion of the water contained in crude is free water that is not dissolved in hydrocarbon.
  • the water is highly dispersed in droplets throughout the oil, thus forming an emulsion.
  • Emulsions have varying characteristics with some emulsions being tightly bound such that it is difficult to separate the water phase from the oil phase.
  • the separation of water from oil can be quite costly. Therefore, there is a need for a cost effective method to remove water from petroleum feed. It would be desirable for this cost effective method to efficiently remove trace amounts of water as well as or after achieving gross separation.
  • Sulfur occurs in many forms in crudes or in light oil, middle oil or other fractions or products.
  • These forms of sulfur can include hydrogen sulfide, organic sulfides, organic disulfides, mercaptans (or thiols), and aromatic ring compounds, such as thiophene, benzothiophene (BT), dibenzothiophene (DBT) (jointly "thiophenic sulfur”) and their alkylated homologues.
  • BT benzothiophene
  • DBT dibenzothiophene
  • Desulfurization of the 4,6-dialkyl dibenzothiophene present in substituted dibenzothiophenes can be extremely difficult.
  • the alkyl substituted dibenzothiophenes are particularly resistant to hydrodesulfurization.
  • Conventional hydrodesulfurization methods to remove sulfur from the residual of a distillation column are often carried out at a temperature over 400 deg C with hydrogen gas applied to the charge.
  • Catalyst such as cobalt and molybdenum on alumina are used to enhance the reaction, as disclosed in US Publication No. 2006-0254956 Al, which is herein incorporated in its entirety.
  • Crude oil varies so greatly by nature, with large differences not only in the hydrocarbon mixture but also in other organic compounds containing heteroatoms such as sulfur, oxygen, nitrogen and metals, such as nickel and vanadium, as well.
  • Most crude oil undergoes distillation processes to refine the crude to desired products. It would be desirable to take advantage of resources available at the production field or at shipside to achieve some degree of desulfurization before transporting the crude for distillation processing.
  • Sulfur compounds are also a consideration in hydroprocessing and hydrotreating.
  • Hydroprocessing refers to the processes in which hydrogen gas is used as part of a conversion of various feedstocks (including aromatics and heavy naphthas) into useful products. Hydroprocessing achieves this outcome through the hydrogenation and the breakup of polynuclear aromatics. Significant portions of these feedstocks are converted through hydrocracking into smaller-sized and more useful product constituents.
  • conventional hydrotreating processes the hydrogenation reactions of aromatic compounds play an important role, mostly because heavy residual compounds are normally aromatic in nature. Therefore, the complete or partial saturation of these compounds by hydrogen addition is an important step in their cracking into smaller, more valuable compounds.
  • Conventional heavy oil hydrocracking processes require relatively high temperatures and high pressures, which are often over 410 deg C and greater than 1000 psi, respectively. Consequently, processing of the crude under more mild conditions would be desirable.
  • Hydrodesulfurization also called hydrotreating, can be effective in reducing the level of sulfur to moderate levels, e.g. 500 ppm, without a severe degradation of olefins or other desirable products.
  • the refractory sulfur compound's DBT dibenzothiophene
  • DBT dibenzothiophene
  • the refractory sulfur compound's DBT can be removed by distillation; however, it requires additional capital expenditure and results in a degraded product, i.e. downgrading a portion of automotive diesel oil to heavy fuel oil.
  • Hydrotreating of any of the sulfur-containing fractions of cracked gasoline causes a reduction in the olefin content.
  • crude oil produced from a well is often in the form of an emulsion consisting of oil and water. Therefore, it would be desirable to separate this emulsion into an oil phase and aqueous phase and then remove the sulfur contained within the oil phase, under moderate process conditions while maintaining the characteristics of the feed stream.
  • the process of the present invention satisfies these needs.
  • the present invention is directed to a method for reducing the sulfur content of a sulfur-containing crude oil stream under mild conditions.
  • the present invention provides a process in which sulfur is removed from a sulfur-containing crude oil feed stream by contacting the crude oil stream with catalyst under sufficient pressure to force the crude oil/catalyst mixture through a filtration medium to provide a product having reduced sulfur content and catalyst-sulf ⁇ ded particles.
  • the catalyst- sulfided particles are then separated from the product to form a product stream that has a reduced sulfur content, and preserves the yield, chemical composition and motor fuel performance characteristics, e.g., octane, of the feed stream,
  • the invention can also include a method for recovering oil from a water- in-oil emulsion.
  • emulsions particularly those containing crude oils
  • the organic acids, asphaltenes, basic nitrogen-containing compounds and solid particles present in the crude oil form an interfacial film at the water/oil interface.
  • the present invention presents a novel and efficient way to break the film and demulsify the emulsion, without the need for demulsifying chemicals, whereby the oil phase is separated and recovered and treated in a cavitation system with catalysts to further enhance its value.
  • the steps of the process include mixing the crude oil feed with a catalyst in a mixer to produce a dispersion stream, the dispersion stream being characterized by dispersion of particles of the catalyst distributed substantially throughout the crude oil feed.
  • the particles defining a particle size range.
  • the particle sizes are substantially in nano particle size range.
  • the dispersion stream is fed to a filtration cavitation system having a cavitation reactor and a filter.
  • a mechanical cavitation system is used to force the dispersion stream under high pressure through the filtration media to upgrade the crude oil.
  • Cavitation can be introduced in a variety of ways known in the art.
  • a preferred embodiment includes inducing cavitation in the filtration cavitation system by pressuring of the dispersion stream through the filter. In one embodiment, this cavitation is induced with mechanical pumps.
  • An alternate embodiment includes inducing cavitation in the filtration cavitation system using transducers. More than one method can be employed at a similar time. In a preferred embodiment, cavitation is induced by applying cavitation vibration having a frequency in the range of about 1 Hz to about 20 kHz to the dispersion stream.
  • Cavitating and filtering the dispersion stream is conducted in the presence of hydrogen gas to produce a mixed stream. Cavitation pressure and cavitation temperature are controlled during the cavitating and filtering step such that the cavitation pressure is maintained substantially within a pre-defined pressure range and the cavitation temperature is maintained substantially within a pre-defined temperature range.
  • the preferred pre-defined temperature ranges is about 40 deg C to about 250 deg C, and the pre-defined pressure range is about 100 psi to about 1000 psi.
  • the cavitating and filtering step is performed for a predetermined residence time sufficient to convert a substantial amount of sulfur in the dispersion stream to catalyst-sulfided' particles. In one embodiment, the pre-defined residence time is in the range of about three (3) seconds to about two (2) hours.
  • the mixed stream is then separated into a spent catalyst stream and a product stream.
  • the spent catalyst stream comprises catalyst-sulfided particles.
  • the product stream being hydrocarbon based and having a substantially reduced sulfur content in comparison with the sulfur content of the crude oil feed. Water, if present, is removed along with the catalyst- sulfided particles.
  • the product stream can be hydrotreated in the presence of hydrogen gas to produce a hydrotreated-product stream.
  • the hydrogen gas is highly pure.
  • the product stream is fed to an equilibrium separator for separating gaseous sulfur products from the product stream to form a usable product, wherein the gaseous sulfur products include hydrogen, hydrogen sulfide and mercaptan.
  • the product stream is split into a recycle stream and an improved product stream.
  • the recycle stream is returned to mix with the dispersion stream and enter the filtration cavitation system for processing.
  • the recycle stream can be returned at any of a variety of points, including, but not limited to, the mixer, upstream of the mixer or directly into the filtration cavitation system.
  • the improved product stream can be fed into the equilibrium separator to remove any gaseous sulfur products.
  • the improved product stream can be subjected to hydrotreating prior to introduction into the equilibrium separator.
  • the catalyst-sulfided particles can be regenerated to form a reformed catalyst stream, and the reformed catalyst stream can then be recycled back into the process at any point upstream the cavitation reactor.
  • the process could further include feeding the product stream to a fluid catalytic cracker in order to increase olefins as compared to the product stream.
  • the process can further include adding a solvent to the crude oil feed prior to the step of cavitating and filtering the dispersion stream.
  • the crude oil produced from a well contains water that is highly dispersed in droplets throughout the crude oil, thus forming an emulsion.
  • Additional features of the invention in various embodiments include delivering cavitation energy to a treatment volume that is comprised of an emulsion, the emulsion further comprising a hydrocarbon and a substrate.
  • the treatment volume may be located either above or below ground. Delivering the cavitation energy to the emulsion imparts energy to electrons and molecular bonds between the hydrocarbon and the substrate. The molecular bonds separate as a result, facilitating demulsif ⁇ cation of the hydrocarbon from the substrate.
  • the process can include sonicating a water-containing crude oil feed in an energy range sufficient to remove a substantial amount of water dissolved in an oil phase of the water-containing crude oil feed to an aqueous phase in the water-containing crude oil feed.
  • the embodiment further includes removing substantially all of the aqueous phase from the water-containing crude oil feed in order to produce the crude oil feed.
  • the energy range sufficient to remove a substantial amount of water dissolved in an oil phase of the water-containing crude oil feed to an aqueous phase in the water-containing crude oil feed is in the range of about 20 to about 250 watts/cm 2 .
  • the process can include subjecting the crude oil feed to sonic energy at a frequency that is in the range of about 400 Hz to about 10 kHz in the presence of a metal hydrogenation catalyst while the crude oil feed is being produced in a production well. Any water contained within the crude oil feed reacts to form hydrogen, which is operable to hydrotreat and upgrade the crude oil feed during production.
  • hydrotreating and upgrading may still be achieved down hole by contacting the crude oil feed with a chemical compound that is selected from the group consisting of ammonia, hydrazine, formic acid, and combinations thereof, and subjecting the crude oil feed to sonic energy within the range of about 400 Hz to about 10 IcHz.
  • the chemical compound contacting the crude oil feed reacts to form hydrogen, and the hydrogen is operable to hydrotreat and upgrade the crude oil feed during production.
  • the metal hydrogenation catalyst is selected from the group consisting of nickel on zinc dust, platinum on carbon, and palladium on carbon.
  • the process for upgrading a water-containing crude oil includes sonicating the water-containing crude oil in an energy range sufficient to create an aqueous phase from water in the water-containing crude oil and removing substantially all of the aqueous phase from the water-containing crude oil in order to produce a crude oil feed.
  • the crude oil feed is then mixed with a catalyst in a mixer to produce a dispersion stream.
  • the dispersion stream being characterized by dispersion of particles of the catalyst distributed substantially throughout the crude oil feed, the particles defining a particle size range.
  • the dispersion stream is fed to a filtration cavitation system having a cavitation reactor and a filter, where it is cavitated and filtered in the presence of hydrogen gas, producing a mixed stream.
  • the cavitation pressure and cavitation temperature are controlled such that the cavitation pressure is maintained substantially within a pre-defined pressure range and the cavitation temperature is maintained substantially within a pre-defined temperature range.
  • the cavitation and filtration step are performed during a pre-determined residence time sufficient to reduce a substantial amount of sulfur in the crude oil.
  • the mixed stream is separated into a spent catalyst stream and a product stream, wherein the spent catalyst stream is made up of at least catalyst-sulfided particles.
  • the product stream is split into a recycle stream and an improved product stream, and the recycle stream is returned to the process to mix with the dispersion stream and enter the filtration cavitation system.
  • the improved product stream is hydrotreated using hydrogen gas to further upgrade the stream and fed into an equilibrium separator to remove gaseous sulfur products yielding a usable product.
  • the properties of the product created by cavitation irradiation in accordance with this invention are significantly improved. Included among these improved properties are the boiling point range, the API gravity, and the sulfur content. Additionally, free water created in accordance with this invention has a reduced content of sulfur as compared to the crude oil feed.
  • FIG. 1 shows one preferred embodiment of the present invention.
  • FIG. 2 shows an alternate embodiment of the invention.
  • FIG. 3 shows an alternate embodiment of the invention.
  • FIG. 4 shows an alternate embodiment of the invention.
  • FIG. 5 shows an alternate embodiment of the invention.
  • FIG. 6 shows an alternate embodiment of the invention.
  • FIG. 7 shows an alternate embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION
  • Embodiments of the present invention include processes of producing an upgraded crude oil from a sulfur containing crude oil.
  • this invention is not limited to the particular combinations and methods disclosed herein. Accordingly, this disclosure is extended to equivalents of combinations and methods as would be recognized by one of ordinary skill in the arts. It should be understood that terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting.
  • crude oil or "hydrocarbon oil” are used to denote any carbonaceous liquid that is derived from petroleum. Included among these liquids are whole crude oil itself and petroleum residuum-based fuel oils including bunker fuels and residual oils.
  • Crude oil has a wide boiling ranges and sulfur content in different fractions.
  • the present invention is particularly useful for feedstocks that can be described as high boiling point feeds of petroleum origin, since these feeds generally contain higher levels of the aromatic sulfur compounds.
  • the exact cut point selected will depend on the sulfur specification for the gasoline product as well as on the type of sulfur compounds present.
  • Sulfur which is present in components boiling below 65 deg C, is mostly in the form of mercaptans and may be removed by extractive type processes, Generally, these feedstocks are: naphtha, gasoil, light cycle oil (LCO), clarified slurry oil (CSO), heavy cycle oil (HCO), thermally cracked stocks, bunker fuels, and vacuum residuum.
  • naphtha includes light naphthas, full naphthas, heavy naphthas or heavy gasoline fractions.
  • Light naphthas typically having a boiling range from about Ce boiling point to about 330 deg F.
  • Full range naphthas typically having a boiling range of about Cs to about 420 deg F.
  • Heavier naphtha fractions boiling in the range of about 260 deg F to 420 deg F, or heavy gasoline fractions boiling within the range of about 330 deg to 5 OQ deg F, preferably about 330 deg F to 420 deg F.
  • Lighter feeds to the process can include a sulfur-containing petroleum fraction, which boils in the gasoline boiling range,
  • the sulfur content of these catalytically or thermally cracked fractions will depend on the sulfur content of the feed to the catalytic or thermal conversion unit as well as on the boiling range of the selected fraction used as the feed in the process. Lighter fractions, for example, will tend to have lower sulfur contents than the higher boiling fractions.
  • gasoil is an uncracked stream, such as gas oil distilled from various petroleum sources,
  • LCO, CSO, and HCO are catalytically cracked stocks.
  • Cycle oils from catalytic cracking processes typically have a boiling range of about 400 deg F to 750 deg F (about 205 deg C to 400 deg C). Because of the high content of aromatics and poisons such as nitrogen and sulfur found in such cycle oils, they require more severe hydrotreating conditions, which can cause a loss of distillate product.
  • thermally cracked stocks include coker gas oils, visbreaker oils or related materials.
  • bunker fuels are heavy residual oils used as fuel by ships and industry and in large-scale heating installations.
  • No. 6 fuel oil which is also known as "Bunker C” fuel oil, is used in oil-fired power plants as the major fuel and is also used as a main propulsion fuel in deep draft vessels in the shipping industry.
  • No. 4 fuel oil and No. 5 fuel oil are used to heat large buildings such as schools, apartment buildings, and office buildings, and as a power source for large stationaiy marine engines.
  • vacuum residuum refers to the heaviest fuel oil from the fractional distillation, commonly referred to as "vacuum resid," with a boiling point of 565 deg C and above. It is typically used as asphalt and coker feed.
  • the present invention is useful in reducing the sulfur content and lowering the molecular weights of any of these fuels and fuel oils.
  • the boiling range of substituted and non-substituted DBT is 530 deg F to 750 deg F. As the percent hydro-desulfurization increases, the relative percentage of DBT increases.
  • API gravity is used herein as it is among those skilled in the art of petroleum and petroleum-derived fuels. In general, the term represents a scale of measurement adopted by the American Petroleum Institute, the values on the scale increasing as specific gravity values decrease.
  • cavitating is used to express that the liquid feed stream containing the metal precursors is contacted with cavitation vibrations (or energy).
  • the cavitation vibrations can be in the cavitation frequency range, i.e. 1 Hz to 20 kHz, or the ultracavitation frequency range, i.e. above 20 kHz.
  • the reactor used to impart cavitation vibrations to the crude oil feed stream can utilize conventional means for producing the cavitation vibrations.
  • nanocatalyst refers to a catalyst in which the mean average diameter of the catalyst is less than 1 micron and greater than 1 nanometer. Upgrading by Cavitation
  • the cavitations serve many functions. Cavitations mix the crude oil feed and catalyst providing for more intimate contact. The cavitation also causes molecular vibrations, with a resulting high pressure and/or high temperature at the molecular level due to the collapse of bubbles, which then causes the metal bonds in the metal precursor to break, resulting in the formation of the metal particles as described herein.
  • the cavitations are generally produced by cavitation generators disposed in the liquid feed stream.
  • Conventional electrocavitation transducers may be employed to generate the cavitation vibrations.
  • the cavitation vibrations can be generated using one or more transducers at a single frequency, a range of different selected frequencies or variable frequencies, i.e., chaotic frequencies.
  • the frequency (or frequencies) of the cavitation vibrations can vary depending upon the composition of the feed stream and the specific catalyst precursor(s) used.
  • one or more transducers can be used to provide cavitation vibrations at characteristic frequencies corresponding to the resonance frequency of the catalysts metal bonds and/or particular carbon-sulfur bonds of the sulfur compounds present in the feed stream,
  • Cavitation vibrations in the cavitation reactor may be provided in a variety of ways, such as the use of "piezo-electro crystals.”
  • the piezo-electro crystals are generally used to provide higher frequency, i.e., cavitation vibrations, and to transmit a single frequency or a very narrow range of frequencies.
  • a cavitation transducer utilizing a terfenol (composed of 90% iron (Fe), 5% dysprosium (Dy), and 5% terbium (Tb)) rod can be used to provide a variable, i.e., selectable, frequency in a broader band range by mechanical shearing.
  • cavitation or advanced cavitation energy which can be created by sonic or ultrasonic waves, on oil emulsions results in separation at the molecular level.
  • Cavitation typically involves the formation and quick collapse of numerous air or vapor pockets (or bubbles) in a liquid through the hydrodynamic generation of rapid and intense pressure changes. This may result from the movement of a solid body, such as a propeller blade or piston. Cavitation can also occur in a hydraulic system as a result of low fluid levels that draw air into the system, producing tiny bubbles that undergo explosive decompression at the pump outlet.
  • cavitation-based ultrasonic energy is believed to activate the organo-sulfur and metallic compounds preferentially.
  • a catalytic material is contacted with the sulfur and heavy metal molecules, while cavitations and optional, external heat are applied.
  • the target compounds are in the petroleum stream, the petroleum stream is brought into contact with the catalytic material.
  • a particular preferred embodiment includes a mechanical filtration cavitation system, which induces cavitation by forcing high pressure fluid through a filtration media; however, those with skill in the art will recognize that various methods of cavitation can be employed within the scope of the invention,
  • the crude oil to be upgraded is subjected to the mechanical filtration cavitation system and is subsequently further upgraded in high purity hydrogen.
  • the various stages of the process of the present invention can be performed either in a batch-wise manner or in a continuous-flow operation. Continuous-flow operations are preferred.
  • the cavitation exposure is performed in a flow through reactor.
  • the invention includes the use of well dispersed catalysts.
  • Catalysts known in the art for hydrotreating and hydroreforming are appropriate, including supported Ni-MO and Co- Mo sulf ⁇ ded catalysts.
  • the metal component of the hydrotreating catalyst may be selected from Groups VIA or Groups VIIIA (IUPAC group identifier) of the Periodic Table.
  • the preferred metals include iron, nickel, cobalt, chromium, vanadium, molybdenum, tungsten, or a combination of metals such as nickel-molybdenum, cobalt-nickel-molybdenum, cobalt- molybdenum, nickel-tungsten, or nickel-tungsten-titanium.
  • the metal component will be selected for good hydrogen transfer activity.
  • the catalyst is selected from the group consisting of Fe, Co, Mo, and Cd.
  • a class of catalysts with high selectivity for middle distillates in less extreme operating conditions is used. Nanocatalysts are also preferred.
  • the process is conducted in an oxygen-free environment following appropriate safety procedures during the first stage of emulsion breaking.
  • the crude oil must be processed in a substantially oxygen free environment.
  • high purity hydrogen is used to treat the materials during cavitation.
  • US Patent No. 7,259,288, entitled “Enhanced Hydrogen Recovery for Hydroproeessing Units” discloses a process to create high purity hydrogen, and is incorporated herein by reference.
  • the organic phase is then recovered from the aqueous phase by conventional separation units and treated with catalyst and hydrogen and upgraded in a cavitation filtrations device, to form a mixed stream, which includes catalyst-sulfided particles and a product stream.
  • the catalyst-sulfid ⁇ d particles are then separated from the mixed stream leaving the product stream.
  • the product stream has a reduced sulfur content and preserves the yield, chemical composition and motor fuel performance characteristics, e.g., octane, of the feed stream.
  • crude oil feed enters mixer [10] via line [2] while the catalyst enters mixer [10] via line [4], Mixer [10] disperses the catalyst throughout the crude oil feed to create a dispersion stream, which exits mixer [10] and enters filtration cavitation system [20] via line [12].
  • Filtration cavitation system [20] is comprised of cavitation reactor [18] and filter [19].
  • the dispersion stream undergoes cavitation and filtration in the presence of first hydrogen gas feed [14], which is preferably highly purified hydrogen gas, to produce a mixed stream.
  • the mixed stream exits filtration cavitation system [20] and enters separator [30] via line [22].
  • Separator [30] can be any suitable device known in the arl for separating catalyst from a hydrocarbon product.
  • the mixed stream is separated into spent catalyst stream [34] and product stream [32], the product stream having a substantially reduced sulfur content in comparison with the sulfur content of the crude oil feed,
  • FIG. 3 the process is the same as the process of FIG. 2, except that product stream [32] is split into two streams: recycle stream [36] and improved product stream [38]. Improved product stream [38] is fed into equilibrium separator [50], while recycle stream [36] is returned to the process to mix with the dispersion stream so that it may subsequently reenter filtration cavitation system [20].
  • crude oil feed enters mixer [10] via line [2] while the catalyst enters mixer [10] via line [4].
  • Mixer [10] disperses the catalyst throughout the crude oil feed to create a dispersion stream, which exits mixer [10] and enters filtration cavitation system [20] via line [12].
  • Filtration cavitation system [20] is comprised of cavitation reactor [18] and filter [19], The dispersion stream undergoes cavitation and filtration in the presence of first hydrogen gas feed [14], which is preferably highly purified hydrogen gas, to produce a mixed stream.
  • the mixed stream exits filtration cavitation system [20] and enters separator [30] via line [22].
  • Separator [30] can be any suitable device known in the art for separating catalyst from a hydrocarbon product.
  • the mixed stream is separated into spent catalyst stream [34] and product stream [32].
  • Product stream [32] is split into two streams: recycle stream [36] and improved product stream [38], Improved product stream [38] is fed into hydrotreater [40], while recycle stream [36] is returned to the process to mix with the dispersion stream so that it may subsequently reenter filtration cavitation system [20].
  • Second hydrogen gas feed [39] enters hydrotreater [40], wherein improved product stream [38] is hydrotreated to produce hydrotreated-product stream [42], wherein hydrotreated-product stream [42] has a substantially reduced sulfur content in comparison with the sulfur content of the crude oil feed.
  • FIG. 5 the process is the same as the process described in FIG. 4, with the addition of feeding hydrotreated-product stream [42] to equilibrium separator [50], wherein gaseous sulfur products [52] are removed from hydrotreated-product stream [42] to produce usable product [54].
  • FIG. 6 the process is the same as the process described in FIG, 1, with the addition of feeding spent catalyst stream [34] to eatalyst regeneration system [70].
  • a suitable gas stream is fed into catalyst regeneration system [70] via line [68].
  • Suitable gas streams are well known in the art, and the selection of a suitable gas stream would depend strongly on the type of catalyst or catalysts being used for treatment.
  • the catalyst-sulflded particles within spent catalyst stream [34] are regenerated within catalyst regeneration system [70], to become reformed catalyst stream [72], which is subsequently returned to the process at mixer [10],
  • One of ordinary skill in the art will recognize acceptable regeneration methods.
  • FIG. 7 represents an embodiment in which a water-containing crude oil feed is treated by a process of the present invention.
  • the water-containing crude oil feed enters sonicator [80] via line [1], wherein the water-containing crude oil feed is subjected to sonications in an energy range sufficient to remove a substantial amount of water dissolved in an oil phase of the water-containing crude oil feed to an aqueous phase in the water-containing crude oil feed forming two-phase stream [82].
  • Two-phase stream [82] enters oil/water separator [90] wherein the water is removed via line [92], leaving behind the crude oil feed, which then enters mixer [10] via line [2],
  • the catalyst enters mixer [10] via line [4].
  • Mixer [10] disperses the catalyst throughout the crude oil feed to create a dispersion stream, which exits mixer [10] and enters filtration cavitation system [20] via line [12J.
  • Filtration cavitation system [20] is comprised of cavitation reactor [18] and filter [19].
  • the dispersion stream undergoes cavitation and filtration in the presence of first hydrogen gas feed [14], which is preferably highly purified hydrogen gas, to produce a mixed stream.
  • the mixed stream exits filtration cavitation system [20] and enters separator [30] via line [22].
  • Separator [30] can be any suitable device known in the art for separating catalyst from a hydrocarbon product.
  • the mixed stream is separated into spent catalyst stream [34] and product stream [32], the product stream having a substantially reduced sulfur content in comparison with the sulfur content of the crude oil feed.
  • Spent catalyst stream [34] then enters water/catalyst separator [60], wherein any excess water that was not removed via line [92] may be removed via line [62], Additionally, water removed via line [62] is upgraded in that the water removed via line [62] has a reduced content of sulfur as compared to water-containing crude oil feed [I].
  • Dehydrated catalyst [64] may then be discarded or sent to a regeneration system and recycled back into the system [not shown].

Abstract

L’invention concerne un procédé de transformation d’une huile brute lourde contenant du soufre en une huile brute plus légère ayant une teneur en soufre réduite et un poids moléculaire réduit. Le procédé est un procédé à basse température qui utilise une cavitation contrôlée.
PCT/US2009/064690 2008-11-19 2009-11-17 Valorisation d’une huile brute acide utilisant des cavitations et des systèmes à base de filtration WO2010059587A1 (fr)

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US8323479B2 (en) 2012-12-04
US8691083B2 (en) 2014-04-08

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